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Synthesis and CharacterizationSynthesis and Characterization of Modified Polyisobutyleney y
Succinimide Dispersants
Y li WYulin WangMay 11, 2010y ,
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OutlineOutlineIntroductionIntroduction
DispersantsObjectivesObjectives
Synthesis of modified PIBSICharacteri ation of modified PIBSICharacterization of modified PIBSI
Experimental ResultsModel reactions1H NMR spectra of PIBSI and modified PIBSI
Future WorkAcknowledgementsg
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Two Major ProblemsSludge Formation
E i F il
Particle Emission
H lth P blEngine Failure Health Problem
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C b D itCarbon Deposits
During normal operation, the engine generates a lot of Ultrafine Particles (UFPs) which have alot of Ultrafine Particles (UFPs) which have a diameter smaller than 100 nm.UFPs are mostly carbon richUFPs are mostly carbon-rich.
Without Dispersant Sludge
CRP<100nm CRP~1μm
High degree of aggregation4
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DispersantsDispersants are amphiphilic. They are composed of two long non-polar chains and a polar head.Dispersants are used in engine oils to prevent theDispersants are used in engine oils to prevent the coagulation of carbon deposits which might block oil flow. They help to stabilize small colloidal particles.
With dispersants
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DispersantsDispersants
Sludge
Without Dispersants With Dispersants6
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bis Polyisobutylene Succinimidebis Polyisobutylene Succinimide (b-PIBSI)( )
2 2
o
Polyisobutylene Succinic Anhydride (PIBSA)
b-PIBSI
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Polyamines used to SynthesizePolyamines used to Synthesize PIBSI
DETAH2N-CH2CH2-NH-CH2CH2-NH2
Di th l t i iDETA Diethylenetriamine~99%
TEPAH2N-(CH2CH2-NH)3-CH2CH2-NH2
Tetraethylenepentamine89%~89%
H N-(CH CH -NH) -CH CH -NHPEHA
H2N-(CH2CH2-NH)4-CH2CH2-NH2Pentaethyelenehexamine
~86%
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Modified PIBSI Dispersant
2
The modified succinimide possesses improved
2
The modified succinimide possesses improved dispersancy properties when used in lubricating oil.
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ObjectivesSynthesize a series of modified bis-polyisobutylene succinimide (M-b-PIBSI)polyisobutylene succinimide (M b PIBSI) dispersantsCh i h difi d diCharacterize the modified dispersantsObtain the critical micelle concentrationObtain the critical micelle concentration(CMC) of the modified dispersants.M d l th d ti f th difi dModel the adsorption of the modified dispersants onto carbon black particles (CBPs).
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S th i P t lSynthesis Protocols
170oCOH H
H
O HH
H170 C Xylenes
PIBSA b PIBSI
2 Hn
N
O
HH
nN
O
HNH m
PIBSA b-PIBSIO
120oC X l
OO
Xylenes
Modified b-PIBSI11
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Fourier Transform InfraredFourier Transform Infrared Spectrometry (FTIR)p y ( )
CH3
1390 cm-14
O O
H N
O
O
NHn
N
O
OHn
C=O
1705 cm-14
C=O
1785 cm-1
700 900 1100 1300 1500 1700 190012
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1H NMR for Polymers
b-PIBSI-DETA has only one secondary amine in the pol meramine in the polymer.Clean and clear spectrum.p
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PIBSA 1H NMR SpectrumPIBSA 1H NMR Spectrum(1)(2) (1)
(2)+(3)
(3)
H3CO
OH H
H
OH H(2)(1)(P1) (P1)
( ) ( )(1)
3
O
HCH2
CH3
CH3
O
O
On
H H
H (2)+(3)
(2)
(1)(P2)
( )
(3)
5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
CH3
(P2)
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
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M d l R ti 1Model Reaction 12 units of MSA were reacted with 1 unit of DETA inxylene at 170oC for 20 hours.Methyl succinimide possess a similar structure as thepolar core of the b-PIBSI-DETA dispersant.
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Model Reaction 1Model Reaction 1PIBSI-DETA Core -CH3
(1)
(3)
(2) (2)+(3) (1)H2O
CDCl3
(5)
(5)
(4)
(2)+(3)+(4)
(1)
7 6 5 4 3 2 1 ppm16
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PIBSA and PIBSIPIBSA and PIBSI(1) (2)
(2)+(3)
(3)
( ) ( )
(1)
H N
OH H
HHN
O HH
H(4)(3)
(1) (2)
(5)(4)
Hn
N
O
Hn
N
ONH(5)
(2)+(3) (1)
7 6 5 4 3 2 1 ppm
5.186
10.730
11.800
91.437
5.187
4.480
29.319
0.616
1.094
0.831
1.000
0.115
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Model Reaction 2:Model Reaction 2:Dibutylamine Reacting with Ethylene Carbonate(1:1 Ratio)
Dibutylamine is reacted with equal amount of
(1:1 Ratio)
Dibutylamine is reacted with equal amount of ethylene carbonate.The reaction is run without any solventThe reaction is run without any solvent.The reaction is run at 120oC.
2 2
3 3
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Model Reaction 2:Model Reaction 2:Dibutylamine Reacting with Ethylene Carbonate
H2 H2 H2 H2(M3)
H3C
2C
CH2
2C
N
2C
CH2
2C
CH3
OO O
H2C
O
CH2
(M1)(M2)
OH
(M1) (M2) (M3)
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm19
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Model Reaction 2:Model Reaction 2:Dibutylamine Reacting with Ethylene Carbonate(1:1 Ratio)
4 Hour Reaction
(1:1 Ratio)
(S3)
H3C
H2C
CH2
H2C
N
H2C
CH2
H2C
CH3
(S1)
( )
H2CCH2
OH
(S1)(S2)
(S1)(S1)
(S2)
(S3)
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm20
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ExtractionThe product mixture wasdissolved in ethyl ether H3C
H2C
CH
H2C
N
H2C
CH
H2C
CH3yand mixed with 1M HClsolution.
H2 H2
O
H2C
O
Both of the ether layerand the water layer wered t t d d th
CH2
OHEther Layer
deprotonated and thendried using MgSO4.At the end the solvents
H2C
H2C
H2C
H2C
HAt the end, the solventswere removed to obtainNMR spectra of each
H3CC
CH2
CN
CCH2
CCH3
H2CCH2p
fraction.2
OHWater Layer21
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Two FractionsTwo FractionsW t F ti
(S3)Water Fraction
(S1)(S2)
Eth F tiH3C
H2C
CH2
H2C
N
H2C
CH2
H2C
CH3
(M3)
Ether FractionO
H2C
O
CH2
OH
(M1)(M2)
OH
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm22
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Ether Layer Separation
Column Chromatography was used toseparate the products in the ether layer.1:1 Ratio of hexane and ethyl acetate wasused as the eluent.Three different compounds were found.
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Column Chromatography toColumn Chromatography to Separate the Ether Layerp y1Ethyl Acetate:1Hexane
(M5)(M3)
(M6)
(M7)
Main Product(M5)
(M7)
(M1)(M2)
M1: 4.2M2: 3.8
(M4)
(M4)
(M3)(M2)(M1)(M5) (M6)
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
6.677
4.557
4.552
1.000
4.557
2.207
2.289
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Ether Layer SeparationEther Layer SeparationSid P d t 1Side Product 1
HBu O
HBu4.31
BuN
CO
CH2
H2C
OC
O
O
H2C
CH2
OC
O
NBu
4.25
4.254.31
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
1.697
2.313
0.093
0.153
0.078
1.000
0.091
0.953
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Ether Layer SeparationEther Layer Separation
H2C
H2C
H2C
H2C
Side Product 2
H3C CH2
N CH2
CH3
OO4 2
H2CCH2
OH2C
OH
4.2
3.6
3.55CH2
4.2
3.63.63.55
4 5 4 0 3 5 3 0 2 5 2 0 1 5 1 0 0 5 ppm4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
1.465
0.994
0.995
0.146
0.219
1.000
0.450
0.964
0.556
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Products in the Model ReactionThere are 5 different compounds found in the reaction mixturereaction mixture.H3C
H2C
CH2
H2C
N
H2C
CH2
H2C
CH3
4.25
O
H2C
O
CH24.23 8
4.31
OH 3.8
2.553.5
4.23.6
273.6
3.55
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Dilute Model Reaction 2Dilute Model Reaction 21g Reaction Mixture dissolved in 10 mL Xylenes
Ether Layer
M1M2
M1 M2
4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
2.908
24.176
6.871
189.675
13.807
2.021
0.813
1.000
0.961
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At the region 3.5 to 4.5, there are only peaks at 3.8 and 4.2, which meansthere is only the main product found in the ether layer of the dilutereaction.
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Dilute Model ReactionDilute Model Reaction1g Reaction Mixture dissolved in 10 mL Xylenes
Water Layer
H C
H2C
C
H2C
N
H2C
C
H2C
CH
(2)
(1)
(4)
H3C CH2
N CH2
CH3
H(1) (3)
(4)
(3) (2)
4 5 4 0 3 5 3 0 2 5 2 0 1 5 1 0 0 5 ppm4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm
1.642
2.226
0.126
1.000
0.065
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There is only DBA found in the spectrum of the water layer product, which means no side product is produced in the dilute reaction.
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Predicted NMR SpectraPredicted NMR Spectra(1)+(2)(3)
(5)
(4)
(2)+(3) (1)(5)
(4)
( )
M1M2
M1 M2
M2
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Spectra of the ModificationSpectra of the Modification Reaction
(1)+(2)(3)
(5)
(4)
(2)+(3)(1)
(5)(4)
(5)
M1
M1M2M2
317.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
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Solvents ComparisonSolvents ComparisonSolvents Boiling Point
(oC)Vapour Pressure(mmHg)
ReactionEfficiency( C) (mmHg) Efficiency
Xylenes 147 18(37.7 oC)
Low yield<10%
Triethylamine 88.8 51.75(20 oC)
Low yieldHigh yield
bt i dobtained occasionally
1 1 2 2-Tetrachloroethane 147 8 React with1,1,2,2 Tetrachloroethane 147 8(20 oC)
React with PIBSIs
N,N-Diisopropylethylamine
127 31(37.7 oC)
Low yield
CH3 CH3
32
H3CCH
NCH
CH3
CH2H3C
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Yield of Modification Reaction of bYield of Modification Reaction of b-PIBSI-DETATemperature
(oC)Triethylamine
( %)Xylenes( %)
Reactant( %)
Time (h )
b‐PIBSI‐DETA:EC R ti
Carbamate Side Ch i Yi ld(oC) (w%) (w%) (w%) (hours) Ratio Chain Yield
130 0% 50% 50% 4 1:2 5%
125 60% 30% 10% 20 1:2 3%125 60% 30% 10% 20 1:2 3%
120 40% 20% 40% 40 1:2 9%
120 50% 25% 25% 40 1:2 8%
120 80% 10% 10% 20 1:2 3%
120 80% 10% 10% 20 1:10 5%
125 15% 70% 15% 20 1:2 1%
120 0% 0% 100% 20 1:2 5%
The yield of the modification of b-PIBSI-DETA is always lower than 10%.The reactions were run in the sealed reaction vessel.
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M difi ti f b PIBSI DETAModification of b-PIBSI-DETA
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm 34
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Modification of m PIBSI DETAModification of m-PIBSI-DETA
7 5 7 0 6 5 6 0 5 5 5 0 4 5 4 0 3 5 3 0 2 5 2 0 1 5 1 0 ppm7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
35
The yield obtained is 13%. It is a big improvement comparing to the yield obtained with b-PIBSI-DETA. The reaction was run with set up 1.
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Polyamines used to SynthesizePolyamines used to Synthesize PIBSI
DETAH2N-CH2CH2-NH-CH2CH2-NH2
Di th l t i iDETA Diethylenetriamine~99%
TEPAH2N-(CH2CH2-NH)3-CH2CH2-NH2
Tetraethylenepentamine89%~89%
H N-(CH CH -NH) -CH CH -NHPEHA
H2N-(CH2CH2-NH)4-CH2CH2-NH2Pentaethyelenehexamine
~86%
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Modification of b-PIBISI-TEPAModification of b PIBISI TEPAOH H
H
O HH
HHn
N
O
HH
nN
O
HNH 2
OH H O HH
Hn
N
O
H
HH
nN
O
H
HN 2
O OH2C
CH2
OH
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 ppm
37The yield obtained is17%.
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MicellesfMicelles are aggregates of dispersants in the solvent.
Depending on the different solvents used, the dispersants form micelles or reverse micellesdispersants form micelles or reverse micelles.Two Important parameters: Critical Micelle Concentration (CMC) and Aggregation Number (Nagg).( ) gg g ( agg)
Reverse Micelles Micelles38
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C iti l Mi ll C t tiCritical Micelle ConcentrationTh CMC i d ith th th i lThe CMC is measured with the ruthenium complex (RuNH2) which probes the dispersant micelles at the molecular level by fluorescencethe molecular level by fluorescence.RuNH2 is soluble in polar solvents (e.g. Acetone), but not soluble in apolar solvents (e.g. Hexane).but not soluble in apolar solvents (e.g. Hexane).
ruthenium bisbipyridine
39
py5-aminophenanthroline hexafluorophosphate
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CMC MeasurementCMC Measurement
After stirring RuNH2 is not solubilised.
RuRuRuRu RuRuRuRu
Ru
Ru
After stirring RuNH2 is solubilised..
RuRuRuRu RuRu
Ru
40
Equal amount of RuNH2 is added into each solution. RuNH2 content of the solution increases when the dispersants form micelles.
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Fluorescence Spectrum of RuNHFluorescence Spectrum of RuNH210)
789
H2
(a. u
.)Dispersant with RuNH2
Dispersant
567
of R
uNH
RuNH2
234
o. In
t. o
01
470 570 670 770
Fluo
470 570 670 770Wavelength (nm)
[PIBSI]=0.13 g/L, [RuNH2]= 4 μM
41
[ ] g , [ ] μThe fluorescence spectrum of PIBSI with RuNH2 was subtracted by thePIBSI spectrum to obtain the fluorescence spectrum of RuNH2.
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Time Study of RuNHTime Study of RuNH2Fluorescence Intensityy
6
7
(a.u
.)
6
7
(a.u
.)
3
4
5
of R
uNH
2(
3
4
5
of R
uNH
2(
1
2
3
Fluo
. Int
. o
1
2
3
Fluo
. Int
. o0
0 1 2 3 4 5 6
F
Time (Day)
00 1 2 3 4 5 6
FTime (Day)
[PIBSI]=1.1 g/L, [RuNH2]=4 μM [M-PIBSI]=0.8 g/L, [RuNH2]=4 μM
42The fluorescence intensity of RuNH2 increases as time increases.
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Preliminary Result of PIBSI CMC
6
7a.
u.)
4
5
uNH
2(a
3
4
t. of
Ru
1
2
Fluo
. In
00.001 0.01 0.1 1
F
[Di t] ( /L)43
[Dispersant] (g/L)
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Conclusions
Model reactions enable the assignmentof 1H NMR spectra of the polymers.Low yields are obtained in theLow yields are obtained in themodification of b-PIBSI-DETA.Hi h d f difi tiHigher degrees of modification areobtained with m-PIBSI-DETA, b-PIBSI-TEPA, and m-PIBSI-TEPA.
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Future Work
Determine the CMC of the modifiedDetermine the CMC of the modifiedPIBSI.
Model the adsorption of the modifiedpPIBSI onto the surface of carbon blackparticles.p
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Acknowledgements
Dr. Jean DuhamelDr. ChongDr Gauthier and Dr TzoganakisDr. Gauthier and Dr. TzoganakisImperial Oil and NSERCEverybody in the Duhamel and Gauthier LabLab.
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Questions?Questions?
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